Process of chloridizing metalliferous materials



condition.of the material in which the .85

i i voids between thembe'gin tobe occupied ma- Patented Nov. 24, 1931 I ramnxina, or rnnmo'n'r, rmsravanm Assrencn rarest carts to ram ant SEPTION OE PITTSBURGH, PENN$YLV QTEEA, A. GQEIQH'ATION F nnnaw' 1 v I a cEss qpcnmnrmzme marannrra cs mar i. arr Breanne,

Y x This invetmsmaee to, chloridizing processesjfor the treatment of metalliferous mate- '3 provide high? extraction yields, are direct,

'mreadily practiced, and more simple than those used at present, and: which are especially applicable to efficient and economical extraction of low grade'materials. i The invention is predicated upon my dis- .135. covery that metal oxides, particularly those "in a reduced form, may beconverted to chloridesdirectby treatment of the oxide metal-1 ,life'rous material in a quasi-Wet condition with gaseous chlorine or hydrogen chloride.

@iKThus, zinc oxide maybe readily and quickly converted .to chloride by subjecting quasiwet material containing itto the action of chlorine or hydrogen chloride, and iron chlorides may be similarly formed, especially from iron oxides in a lower stage of oxidation.

Also, in accordance with the invention, chlorides formed'inthis manner, such as those of iron, exert a powerful chloridizing efl'ect As used herein the term quasi-wet is applied to concisely refere to a dampened particles are moistened with liquid, butin which I there is insuificient liquid present to occupy the intersticesbetween the particles, or to i t seep orpercolate through the ore mass. This degree of moistening' does not, in general, cause agglomeration of the particles, and the surfaces of all particles are, exposed to the action of thechlorine. There is a maximum i tur content, varying with d fferent ores,

3 above which the ore volume'diminishes rapidly -and thefparticles' agglomerate as the terial'ly with liquid This provides a ready I test-ofthe quasi-wet condition.

j a neanen filed April 5,

. they mesh or finer may yupon other-metals,. particularly when they I r @323.

1930. Serial no. tantra "fact that the small amount of liquid used is I quickly and readily saturated with the chlorine or hydrogen chloride used, thus forming a'concentrated reagent solution in intimate contact with all parts of the particles. It likewise may act to dissolve the chlorides as are formed, not only to keep fresh surfaces exposed to attack by the reagent gas, but also topermit reaction of the chloride upon other constituents of thematerial.

- The invention is especially applicable to metalliferous materials containing oxide, and

particularly to those containing 1ron. It is applicable to such materials generally, for example, ores, mine dumps, and the like.

In its preferred embodiments the materials are finely divided, and the finer the material, the more rapid and profound the attack by chlorine or hydrogen chloride will be. ln most instances, division to pass 100 or 140- mesh will sufice, although material of 200- be used, reference being here made to the sieve specifications adopted by the U. S. Bureau of Standards.

In the practice of the invention with materials largely in the form of oxides, the material is treated with liquid in an amount sufficient to render it quasi-wet, and the quasi- Wet material is then treated with chlorine or hydrogen chloride, after which the metal values may be extracted with simple solvents. With some materials the vchloridizing action is so'rapid and profound as to cause heating of the material, but in the case of materials containing small amounts of metals, it is advisable to heat gently during treatment. In the specification and claims it will be understood that when chlorine is referred to, hy-

drogen chloride or mixtures containing chloas aqueoussolutions of chlorine or sodium.

chloride, may also be used. Satisfactory recove ies are obtained with oxide materials by treating with chlorine in an amount sufiicient to saturate the ore mass.

Where the oxide material to be treated con- 7 tains sulfide sulfur, it is usually necessary to break up the sulfide molecule in order to obtain complete recovery of the metal values. This may be effected by exposure of the quasiwet material to an oxidizing atmosphere, for example air, after treatment with chlorine.

I have found, however, that when iron chlorides in such materials are decomposed by heat the sulfide radical in the ore is readily broken down and the metal converted to chloride by the hot nascent hydrogen chloride and chlorine formed. in breaking downiron chloride. The sulfur, is largely or wholly volatilized as hydrogen sulfide, sulfur vapor,

or sulfur com ounds of chlorine, .from which elemental sul ur may be recovered.

Most metalliferous materials contain iron in uantities sufficient to produce this action, and because the reactions are rapid and effective, this procedure is preferred for conversion to readily soluble chlorides of the metallic sulfides. A further benefit of this procedure resides in conversion of iron chlorides to oxides which are insoluble in the simple solvents used to leach out the metal value chlorides. This reduces contamination of the leach liquors and materially simplifies their subsequent treatment.

Although es ecially a plicable to oxide materials, the enefits o the invention are equally obtainable with high sulfide ores by subjecting the material .to an oxidizing roast and then treating it in the manner described hereinabove.

The addition of a halide, preferably a chloride, such as common salt, to the'material before heat treatment is beneficial, because it provides for production of chlorine or -chloamount of chlorine needed may be reduced, and sufficient chlorine to complete chloridizin of the metal values is provided.

eat treatment is preferably conducted in a muflle furnace, using a limited amount of air, or no air at all, at a'temperature sulficient to decompose the iron chloride. ,Reaction will generally begin at about 100 0., and in the preferred embodiment the material is heated at about 100 to 200 C. for aperiod of time varying with the type of material being treated. If suflicient iron chloride is present, any metal present as residual sulfide is converted to chloride during this treatment. Hydrogen chloride and steam are evolved during this heating, and because the former is liberated in a nascent con dition, it exerts a powerful action on the metal values, whether present as metal or as sulfide, oxide, carbonate, silicate, or the like. The reactions probably are: Moist iron chlorides+heat=iron oxides-t nascent (HCl+Cl) When the sulfides have been broken up, the temperature is raised to about 200 to 300 C.,

rides during heating. In this manner the.

and, in general, two hours heating at this temperature suffices, during which time further amounts of h drogen chloride, and some chloform. The ferrous chloride thus formed then acts as a strong chloridizing agent. Other metal compounds are also attacked and made soluble, and the procedure is especiall efli-- cacious in rendering refractory gol and silver ores, and zinc complexes, amenable to extraction. It also further reduces the amount of chlorine needed. In general, this procedure, may be practised under pressures of from about 1 to 5 pounds gauge, at temperatures from about 100 to 150 0., although the reactions will be more rapid at higher pressures and temperatures.

After treatment such metals as copper, manganese, cadmium, cobalt, nickel, etc.

may be leached out with water, and lead with dilute caustic soda solution. Silver may be extracted with hyposulfate or cyanide, but where gold is present it is sometimes attacked only partially during treatment, and it will usually be more desirable to cyanide these metals after leaching out the base inetals. Where considerable amounts of zinc are present it is advisable to leach out the zinc chloride formed before heat treatment.

E azample 1.A sulfide ore containing about 20 per cent of copper, 12 per cent of antimony and 8 ounces of silver per ton, together with iron and other usual impurities,

was ground to QOO-mesh, roasted 3 hours below 47 5 (1, rendered quasi-wet with water to hydrate the salts which had formed in roasting, and roasting was then completed. The roasted ore was then ground to approximately QOO-mesh, after which it was placed in cold 4 per cent I-LSO, solution and agitated with air for 6 hours, followed by thorough washing with water to remove the bulk of the copper. The ore was then dried until its water content was just sufiicient to render it quasi-wet, when it was mixed with 3 per cent by weight of sodium chloride and treated with chlorine, followed by heating in a closed muffle for 3 hours at 100 to 150 U., during which time considerable steam and hydrogen chloride evolved, together with a little chlorine. The ore was turned over every 10 minutes, air being simultaneously admitted for one minute.- The temperature wasthen increased during 3 hours to about 400 to 450 0., and at the end of this time diminished evolution of fume showed that the decomposition of iron chlorides was practically complete. When cool the ore was tion..

A particularly efi'ective manner of practis'ing the invention is to pass the material to the to hearth of a multiple hearth muffle type urnace arranged for up draft. As the material passes over the lower hearths it is subjected to the heat treatment dematerial, and the hydrogen chloride and scribed, and the gases liberated pass upwardly over incoming material, The steam in the gases is condensed on the incoming chlorine in the gases combine with the now quasi-wet ore to form iron chlorides which, as the material reaches-the hotter part of the furnace, are in turn broken down, liberating chlorine and hydrogen chloride which pass upwardly and react withnew amounts of material. By suitable regulation of heat the material discharged from the furnace is ready for leaching. 7

As previously mentioned, iron is beneficial to the processes provided by the invention. The invention is particularly applicable also to materials having a high iron content, and not only are sulfur and the metal values, such ammanganese and nickel removed, but also metalloids, such as'phosphorous. The heat treatment converts iron chlorides formed in processing to oxides, and the residual material consists of practically pure iron oxide. and silica. Accordingly the invention provides for eficient beneficiation of iron ore materials, to adapt both low and high grade iron ores for the production of purer irons and steels.

Example 9.As showing the applicability of the invention to beneficiation of iron ores, the following actual test is cited. An ore containing 25 to 30 per cent of sulfur, about- 40 per cent of iron, 3.64 per cent of nickel,-

0.26 per cent of copper, and 0.3 per cent of cobalt, with small amounts of arsenic and phosphorous, was ground to 200-mesh, roasted 3 hours below 47 5 (1, reground to approximately 200-mesh, and leached with cold 4 per cent H 80 solution, followed by washing with water, to wash sulfates out completely. The ore was then dried until it contained about 15 percent of water, which rendered it just quasi-wet, and it was then treated with chlorine. The ore was stirred ahd owing to the evolution of a large amount of heat it was necessary to restrict the rate of chlorine addition.

The ore was then heat treated in the same manner as that described in Example 1, and after leaching with hot water analysis of the residue showed practicall all of the sulfur and phosphorous to have een removed, and that its content of metallic impurities was:

' Percent Copper 0.02 Cobalt 0.08 Nickel 0.11

The leach liquor contained practically all of the copper, cobalt and nickel, and it showed only a trace of iron.

The chloridizing reactions in the processesprovided by the invention are vigorous and profound, and the invention thus provides processes in which cliloridizing is eifected directly, simply and at low cost,-to obtain high or substantially complete recoveries of the metal values.

Further economies may be eiiected by reuse of the hydrogen chloride liberated in heat treatment. It may be returned to the system to act upon fresh material, as a substitute for part or all of the chlorine, or it maybe converted to chlorine by well known methods. For example, the fume may be passed over heated bricks saturated withcopper chloride-this mode of producing chlorine being sufiiciently effective for this purpose.

The process of beneficiating iron ores is claimed in a copending application filed by me of even date herewith.

According to the provisions of the patent statutes, l have explained the principle and mode of operation of my invention, and have described What It now consider to represent its best embodiments. However, I desire to have it understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically described.

1 claim 1. A process of chloridizing oxide ore in steps, comprising applying liquid to the finely divided ore to bring it to quasi-wet condition, treating it while quasi-wet with chlorine to form metal chloride distributed therein, then treating with restricted amounts of air at temperatures between 100 C. and 200 (1, and then heating it with chlorine and steam to above 350 C. to continue the chloridization.

2. A process of gradual chloridization of oxide ore containing iron, comprising applying liquid to the finely divided ore to bring it to quasi-wet'condition, treating it while quasi-wet with chlorine to form iron chlorides above 350 C. in the presence of chlorine and steam to continue the chloridization.

3. A process of chloridizing sulfide ore containing iron, comprising converting the ore to oxide, then at normal temperatures applying liquid to the finely divided ore to bring it to: quasi-wet condition, treating it while quasi- 5 wet with chlorine to form iron chlorides distributed therein, then agitating the ore with restricted amounts of .air at temperatures between 100 C. and 200 C., and continuing the heating to above 350 C. while introducing chlorine and "steam to continue the chloridization.

In testimony whereof, I sign my name;

RALPH F. MEYER. 

